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EP0480281B1 - Colerants du type indophenol et un procédé pour leurs transfert thermique - Google Patents

Colerants du type indophenol et un procédé pour leurs transfert thermique Download PDF

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Publication number
EP0480281B1
EP0480281B1 EP91116656A EP91116656A EP0480281B1 EP 0480281 B1 EP0480281 B1 EP 0480281B1 EP 91116656 A EP91116656 A EP 91116656A EP 91116656 A EP91116656 A EP 91116656A EP 0480281 B1 EP0480281 B1 EP 0480281B1
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Prior art keywords
alkyl
hydrogen
interrupted
ether function
phenyl
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EP91116656A
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German (de)
English (en)
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EP0480281A1 (fr
Inventor
Volker Dr. Bach
Karl-Heinz Dr. Etzbach
Ruediger Dr. Sens
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BASF SE
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BASF SE
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/382—Contact thermal transfer or sublimation processes
    • B41M5/385—Contact thermal transfer or sublimation processes characterised by the transferable dyes or pigments
    • B41M5/3856—Dyes characterised by an acyclic -X=C group, where X can represent both nitrogen and a substituted carbon atom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B53/00—Quinone imides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/382—Contact thermal transfer or sublimation processes
    • B41M5/385—Contact thermal transfer or sublimation processes characterised by the transferable dyes or pigments
    • B41M5/3854—Dyes containing one or more acyclic carbon-to-carbon double bonds, e.g., di- or tri-cyanovinyl, methine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/382—Contact thermal transfer or sublimation processes
    • B41M5/385—Contact thermal transfer or sublimation processes characterised by the transferable dyes or pigments
    • B41M5/39—Dyes containing one or more carbon-to-nitrogen double bonds, e.g. azomethine

Definitions

  • the object of the present invention was to provide new indophenol dyes which have advantageous performance properties.
  • alkyl groups occur in the abovementioned formula I, z. B. cyano, C 1 -C 6 alkanoyloxy, C 1 -C 4 alkoxycarbonyl or C 1 -C 4 alkoxycarbonyloxy, in which case the alkoxy group may be substituted by phenyl or C 1 -C 4 alkoxy come.
  • the substituents e.g. Methyl, chlorine, methylsulfonylamino or acetylamino come into consideration.
  • the benzo ring is therefore usually substituted once or twice.
  • Suitable radicals R 1 , R 2 and R 5 are e.g. B. methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, octyl or 2-ethylhexyl.
  • R 1 and R 2 are furthermore, for example, 2-cyanoethyl, 2- or 3-cyanopropyl, 2-acetyloxyethyl, 2- or 3-acetyloxypropyl, 2-isobutyryloxyethyl, 2- or 3-isobutyryloxypropyl, 2-methoxycarbonylethyl, 2- or 3 -Methoxycarbonylpropyl, 2-ethoxycarbonylethyl, 2- or 3-ethoxycarbonylpropyl, 2-methoxycarbonyloxyethyl, 2- or 3-methoxycarbonyloxypropyl, 2-ethoxycarbonyloxyethyl, 2- or 3-ethoxycarbonyloxypropyl, 2-propoxycarbonyloxyethyl, 2- or 3-propoxycarbonyloxypropyl, 2-butoxycarbon , 2- or 3-butoxycarbonyloxypropyl, 2- (2-phenylethoxycarbonyloxy) ethyl, 2- or 3-butoxycarbonyloxyprop
  • R 1 and R 2 are furthermore, for example, 2-methoxyethyl, 2- or 3-methoxypropyl, 2-ethoxyethyl, 2- or 3-ethoxypropyl, 2-propoxyethyl, 2- or 3-propoxypropyl, 2-butoxyethyl, 2- or 3 -Butoxypropyl, 3,6-dioxaheptyl or 3,6-dioxaoctyl.
  • Suitable radicals R 4 are z.
  • B methyl, ethyl, propyl or butylsulfonylamino, mono- or dimethyl, -ethyl, -propyl- or -butylaminosulfonylamino.
  • R 5 radicals are furthermore, for example, phenyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-ethylphenyl, 2-, 3- or 4-propylphenyl, 2-, 3- or 4-isopropylphenyl, 2- , 3- or 4-butylphenyl, 2,4-dimethylphenyl, 2-, 3- or 4-methoxyphenyl, 2-, 3- or 4-ethoxyphenyl, 2-, 3- or 4-isobutoxyphenyl or 2,4-dimethoxyphenyl.
  • the residues Q are derived from a five-membered aromatic heterocyclic residue which is selected from the group consisting of pyrazole, imidazole, oxazole, isoxazole, thiazole, isothiazole, indazole, benzimidazole, benzoxazole, benzisoxazole, benzothiazole and benzisothiazole.
  • heterocycles from the imidazole, pyrazole, thiazole, isothiazole or benzimidazole series are heterocycles from the imidazole, pyrazole, thiazole, isothiazole or benzimidazole series.
  • L 1 , L 2 , L 3 and L 5 are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpenyl, heptyl, octyl or 2-ethylhexyl.
  • L 2 and L 5 are furthermore, for example, 2-methoxyethyl, 2- or 3-methoxypropyl, 2-ethoxyethyl, 2- or 3-ethoxypropyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, pentyloxy, isopentyloxy , Neopentyloxy, hexyloxy, heptyloxy, octyloxy or 2-ethylhexyloxy.
  • L 5 radicals are furthermore, for example, methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, pentylthio, hexylthio, heptylthio or octylthio.
  • L 2 , L 3 and L 4 are furthermore, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, 2-methoxyethoxycarbonyl, 2-ethoxyethoxycarbonyl, 3,6-dioxaheptyloxycarbonyl or 3,6-dioxaoctyloxycarbonyl.
  • indonaphthol dyes of the formula I in which K corresponds to the formula IIa or IIc are particularly preferred.
  • the indophenol dyes of the formula I according to the invention can be prepared by methods known per se.
  • a nitroso compound of formula IV wherein R 1 , R 2 , R 3 and R 4 each have the meaning given above, with a phenol compound of the formula V. in which Q and the ring A each have the abovementioned meaning, condense (see, for example, DE-A-3 716 656).
  • Another object of the present invention was to provide a new process for the thermal transfer of dyes.
  • a transfer sheet which contains a thermally transferable dye in one or more binders, optionally together with suitable auxiliaries, on a support, with an energy source, e.g. a heating head or a laser, heated by short heating pulses (duration: fractions of a second) from the back, whereby the dye migrates on the transfer sheet and diffuses into the surface coating of a recording medium.
  • an energy source e.g. a heating head or a laser
  • the color recording is carried out using the three subtractive primary colors yellow, magenta, cyan (and possibly black).
  • the dyes transferred in the process according to the invention are generally distinguished by improved migration properties in the recording medium at room temperature, easier thermal transferability, higher thermal and photochemical stability, easier technical accessibility, better resistance to moisture and chemical substances, higher color strength, better solubility or higher color purity.
  • the dyes of the formula I used in the new process are advantageously suitable for the production of a trichromatic system required for subtractive color mixing.
  • the dyes are processed into a printing ink in a suitable organic solvent or in mixtures of solvents with one or more binders, if appropriate with the addition of auxiliaries.
  • a printing ink in a suitable organic solvent or in mixtures of solvents with one or more binders, if appropriate with the addition of auxiliaries.
  • the printing ink can be applied to the inert support using a doctor blade and the dyeing can be dried in air.
  • Suitable organic solvents for the dyes I are e.g. those in which the solubility of the dyes I at a temperature of 20 ° C. is greater than 1% by weight, preferably greater than 5% by weight.
  • Examples include ethanol, propanol, isobutanol, tetrahydrofuran, methylene chloride, methyl ethyl ketone, cyclopentanone, cyclohexanone, toluene, chlorobenzene or mixtures thereof.
  • binders All resins or polymer materials which are soluble in organic solvents and are capable of binding the dyes to the inert support in an abrasion-resistant manner are suitable as binders. Preference is given to those binders which, after the printing ink has dried in air, absorb the dye in the form of a clear, transparent film without the dye crystallizing out visibly.
  • binders examples include cellulose derivatives, e.g. Methyl cellulose, ethyl cellulose, ethyl hydroxyethyl cellulose, hydroxypropyl cellulose, cellulose acetate or cellulose acetobutyrate, starch alginates, alkyd resin, vinyl resin, polyvinyl alcohol, polyvinyl acetate, polyvinyl butyrate or polyvinyl pyrrolidone.
  • Polymers and copolymers of acrylates or their derivatives, such as polyacrylic acid, polymethyl methacrylate or styrene-acrylate copolymers, polyester resin, polyamide resin, polyurethane resin or natural CH resin, such as gum arabic are also suitable as binders.
  • Other suitable binders are e.g. in DE-A-3 524 519.
  • Preferred binders are ethyl cellulose, ethyl hydroxyethyl cellulose, polyvinyl butyrate or polyvinyl acetate.
  • the weight ratio of binder: dye is generally 1: 1 to 10: 1.
  • Inert carriers are e.g. B. tissue, blotting paper or glassine paper or plastic films with good heat resistance, e.g. B. optionally metal-coated polyester, polyamide or polyimide.
  • the inert carrier is optionally additionally coated with a slip layer on the side facing the thermal head in order to prevent the energy source, in particular the thermal head, from sticking to the carrier material.
  • Suitable lubricants are e.g. in EP-A-216 483 or EP-A-227 095.
  • the thickness of the dye carrier is generally 3 to 30 microns, preferably 5 to 10 microns.
  • the dye receiving layer e.g. B. modified polycarbonates or polyester.
  • Suitable formulations for the receiver layer composition are e.g. in EP-A-227 094, EP-A-133 012, EP-A-133 011, EP-A-111 004, JP-A-199 997/1986, JP-A-283 595/1986, JP- A-237 694/1986 or JP-A-127 392/1986 described in detail.
  • the transmission takes place by means of an energy source, for example by means of a laser or preferably by means of a thermal head, the latter being based on a temperature of ⁇ 300 ° C must be heatable so that the dye transfer can take place in the time range t: 0 ⁇ t ⁇ 15 msec.
  • the dye migrates from the transfer sheet and diffuses into the surface coating of the recording medium.
  • the dyes according to the invention are furthermore advantageously suitable for dyeing synthetic materials, e.g. of polyesters, polyamides or polycarbonates. Textile fabrics made of polyester or polyamide or polyester-cotton blended fabrics should be mentioned in particular.
  • the new dyes are also advantageous for the production of color filters, such as those e.g. are described in EP-A-399 473.
  • nitroso compound was taken up in methylene chloride, added to a solution of 3.7 g of phenol (a) in 35 ml of methylene chloride and 37 ml of acetic anhydride, and stirring was continued at room temperature until the reaction was complete (TLC control). 100 ml of water were then added, the mixture was heated to 40 ° C. for 1 hour and then the methylene chloride was largely distilled off.
  • the dyes listed in Table 2 below were processed according to ⁇ ) and the resulting, dye-coated supports according to ⁇ ) tested for the transfer behavior.
  • the table shows the thermal transfer parameters T * and ⁇ E T as well as the weight ratio of dye: binder.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)

Claims (3)

  1. Colorants de la famille des indophénols de formule I
    Figure imgb0048
     dans laquelle
    X   représente un atome d'azote,
    Q   représente un reste hétérocyclique aromatique à cinq maillons qui dérive d'un hétérocycle choisi dans le groupe constitué par le pyrazole, l'imidazole, l'oxazole, l'isoxazole, le thiazole, l'isothiazole, l'indazole, le benzimidazole, le benzoxazole, le benzisoxazole, le benzothiazole et le benzisothiazole, et
    K   représente un reste de formule
    Figure imgb0049
    Figure imgb0050
    Figure imgb0051
    Figure imgb0052
    où
    R1 et R2   sont identiques ou différents et sont mis chacun, indépendamment l'un de l'autre, pour un atome d'hydrogène, pour un reste alkyle en C1-C8 qui est éventuellement substitué et peut être interrompu par un ou deux atomes d'oxygène en fonction éther, ou pour un reste cycloalkyle en C5-C7,
    R3   est mis pour un atome d'hydrogène ou pour un reste méthyle, éthyle, méthoxy ou éthoxy,
    R4   est mis pour un atome d'hydrogène ou pour un reste méthyle, méthoxy, alkylsulfonylamino en C1-C4, mono- ou di(alkyl en C1-C4)-aminosulfonylamino ou pour le reste -NHCOR8 ou -NHCO2R8, R8 représentant chaque fois un groupement phényle, benzyle, tolyle ou alkyle en C1-C8 qui est éventuellement interrompu par un ou deux atomes d'oxygène en fonction éther,
    R5   est mis pour un atome d'hydrogène, d'halogène ou pour un reste alkyle en C1-C8, phényle éventuellement substitué par un groupement alkyle en C1-C4 ou alcoxy en C1-C4, benzyle éventuellement substitué par un groupement alkyle en C1-C4 ou alcoxy en C1-C4, cyclohexyle, thiényle, hydroxy ou mono(alkyl en C1-C8)amino,
    R6   est mis pour un atome d'hydrogène ou un reste méthyle et
    R7   est mis pour un atome d'hydrogène ou un reste
       méthyle, méthoxy ou acétylamino, et le noyau A peut être condensé par un noyau benzénique éventuellement substitué.
  2. Colorants de la famille des indophénols selon la revendication 1, caractérisés en ce que Q est mis pour un reste de formule
    Figure imgb0053
     dans laquelle
    L1   représente un atome d'hydrogène ou un reste alkyle en C1-C8, benzyle, cyclohexyle, phényle ou tolyle,
    L2   représente un atome d'hydrogène, de chlore ou un reste alkyle en C1-C8 qui est éventuellement interrompu par un atome d'oxygène en fonction éther, phényle, alcoxy en C1-C8, cyano ou (alcoxy en C1-C8)carbonyle, le groupement alkyle pouvant être interrompu par un ou deux atomes d'oxygène en fonction éther,
    L3   représente un atome d'hydrogène ou un reste alkyle en C1-C8, phényle, cyano, nitro ou (alcoxy en C1-C8)carbonyle, le groupement alkyle pouvant être interrompu par un ou deux atomes d'oxygène en fonction éther, ou L2 et L3 représentent ensemble un noyau benzénique condensé,
    L4   représente un atome d'hydrogène, de chlore ou un reste cyano, nitro ou (alcoxy en C1-C8)carbonyle, le groupement alkyle pouvant être interrompu par un ou deux atomes d'oxygène en fonction éther, et
    L5   représente un atome de chlore ou un reste alkyle en C1-C8 qui est éventuellement interrompu par un atome d'oxygène en fonction éther, alcoxy en C1-C8 ou alkylthio en C1-C8.
  3. Procédé de transfert de colorants de la famille des indophénols entre un support et un papier revêtu de matière plastique, par diffusion ou sublimation à l'aide d'une source d'énergie, caractérisé en ce que l'on utilise un support sur lequel se trouvent un ou plusieurs colorants de la famille des indophénols de formule I selon la revendication 1.
EP91116656A 1990-10-08 1991-09-30 Colerants du type indophenol et un procédé pour leurs transfert thermique Expired - Lifetime EP0480281B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4031804 1990-10-08
DE4031804A DE4031804A1 (de) 1990-10-08 1990-10-08 Indophenolfarbstoffe und ein verfahren zu ihrer thermischen uebertragung

Publications (2)

Publication Number Publication Date
EP0480281A1 EP0480281A1 (fr) 1992-04-15
EP0480281B1 true EP0480281B1 (fr) 1996-08-28

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EP91116656A Expired - Lifetime EP0480281B1 (fr) 1990-10-08 1991-09-30 Colerants du type indophenol et un procédé pour leurs transfert thermique

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US (1) US5225548A (fr)
EP (1) EP0480281B1 (fr)
JP (1) JP2930785B2 (fr)
DE (2) DE4031804A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4218359A1 (de) * 1992-06-04 1993-12-09 Basf Ag Polymerisate, die Methin- oder Azamethinfarbstoffe enthalten
DE4440486A1 (de) * 1994-11-12 1996-05-15 Basf Ag Azamethinfarbstoffe
DE19512398A1 (de) * 1995-04-03 1996-10-10 Basf Ag Azamethinfarbstoffe mit heterocyclischen Seitengruppen
US7541475B2 (en) 2003-07-30 2009-06-02 Abbott Laboratories Substituted thiazoles
US20050027128A1 (en) * 2003-07-30 2005-02-03 Robbins Timothy A. Substituted thiazoles

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0717107B2 (ja) * 1985-05-23 1995-03-01 大日本印刷株式会社 熱転写シ−ト
US4695287A (en) * 1985-12-24 1987-09-22 Eastman Kodak Company Cyan dye-donor element used in thermal dye transfer
DE3716656A1 (de) * 1987-05-19 1988-12-01 Basf Ag Thienonverbindungen
US4769360A (en) * 1987-09-14 1988-09-06 Eastman Kodak Company Cyan dye-donor element for thermal dye transfer
DE3929698A1 (de) * 1989-09-07 1991-03-14 Basf Ag Triazolopyridinfarbstoffe sowie ein verfahren zum thermischen transfer von methinfarbstoffen

Also Published As

Publication number Publication date
JP2930785B2 (ja) 1999-08-03
EP0480281A1 (fr) 1992-04-15
US5225548A (en) 1993-07-06
DE4031804A1 (de) 1992-04-09
JPH04234460A (ja) 1992-08-24
DE59108117D1 (de) 1996-10-02

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